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Kinetics for the photo-chemical degradation of Methyl butyrate in presence of Cl atoms and OH radicals

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Abstract

The Cl/OH initiated temperature dependent photo-oxidative reaction kinetics of methyl butyrate (MB) were examined using a relative rate (RR) technique. Gas chromatography with flame ionization and mass spectrometric detection were used to monitor the concentration of the reactants and to identify the products. The temperature dependent kinetics of MB with Cl atoms were measured with respect to the reaction of Cl with C2H 6 and C2H4. The temperature dependent kinetics for the reaction of MB with OH radicals were measured using n- propanol and iso -propanol as references. The obtained rate coefficients for the Cl and OH reactions with MB are, k Cl(Expt) (T) = [(7.76 ± 0.47) × 10 −11] exp [(10.31 ± 0.20)/T] cm3 molecule−1 s−1 and k OH(Expt) (T) = [(4.32 ± 0.21) × 10 −12] exp [-(25.26 ± 0.39)/T] cm3 molecule−1 s−1 respectively. Dual level direct dynamics were used to perform the computational calculations to further elucidate the mechanisms over the studied temperature range. The rate coefficients for H-abstraction reactions were computed using Canonical Variational Transition State Theory with Small Curvature Tunneling (CVT/SCT) with Interpolated Single Point Energies (ISPE) method. The rate coefficients over the studied temperature range yielded the Arrhenius equations: k Cl(Theory) (200–400 K) = [(4.05 ± 0.54) × 10–11] exp [-(2.80 ± 0.11)/T] cm3 molecule−1 s−1 and k OH(Theory) (200–400 K) = [(1.96 ± 0.68) × 10 -11] exp [-(384 ± 38)/T] cm3 molecule −1 s −1. Possible degradation mechanisms for the reactions are proposed based on the observed products. Thermo-chemical parameters, ozone formation potential, branching ratios, and the atmospheric lifetime of MB are calculated to understand the fate of MB in the atmosphere.

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References

  • Andersen, V.F., Ørnsø, K.B., Jørgensen, S., Nielsen, O.J., Johnson, M.S.: Atmospheric chemistry of ethyl propionate. J. Phys. Chem. A 116, 5164–5179 (2012)

    Article  Google Scholar 

  • Atkinson, R., Baulch, D.L., Cox, R.A., Crowley, J.N., Hampson, R.F., Kerr, J.A., Rossi M.J., Troe, J.: Summary of Evaluated Kinetic and Photochemical Data for Atmospheric Chemistry, Web Version, (2001)

  • Balan, R.C., Balla, R.: Cl-initiated photo-oxidation reactions of methyl propionate in atmospheric condition. Env. Sci. Pollut. Res. 25, 20999–21010 (2018)

    Article  Google Scholar 

  • Bufalini, J.J., Walter, T.A., Bufalini, M.M.: Ozone formation potential of organic compounds. Environ. Sci. Technol. 10, 908–912 (1976)

    Article  Google Scholar 

  • Carlton, A.G., Turpin, B.J., Lim, H.J., Altieri, K.E., Seitzinger, S.: Link between isoprene and secondary organic aerosol (SOA): Pyruvic acid oxidation yields low volatility organic acids in clouds. Geophys. Res. Lett. 33(6), (2006)

  • Carter, W.P.: Computer modeling of environmental chamber measurements of maximum incremental reactivities of volatile organic compounds. Atmos. Environ. 29, 2513–2527 (1995)

    Article  Google Scholar 

  • Chance, K., Palmer, P.I., Spurr, R.J., Martin, R.V., Kurosu, T.P., Jacob, D.J.: Satellite observations of formaldehyde over North America from GOME. Geophys. Res. Lett. 27(21), 3461–3464 (2000)

    Article  Google Scholar 

  • Charlson, R.J., Schwartz, S.E.: Climate forcing by anthropogenic aerosols. Science 255, 423 (1992)

    Article  Google Scholar 

  • Cheramangalath Balan, R., Rajakumar, B.: Kinetic and Mechanistic Investigation. J. Phys. Chem. A, Cl Atom Initiated Atmospheric Degradation of Saturated Cyclic Hydrocarbons 7361–7373 (2019)

  • Cheramangalath Balan, R., Rajakumar, B.: Photo Oxidation Reaction Kinetics of Ethyl Propionate with Cl Atom and Formation of Propionic Acid. J. Phys. Chem. A 122, 8274–8285 (2018)

    Article  Google Scholar 

  • Coquet, S., Ariya, P.A.: Kinetics of the Gas-phase Reactions of Cl Atom with Selected C2–C5 Unsaturated Hydrocarbons at 283< T< 323 K. Int J Chem Kinet. 32, 478–484 (2000)

    Article  Google Scholar 

  • Cuevas, C.A., Notario, A., Martínez, E., Albaladejo, J.: Influence of temperature in the kinetics of the gas-phase reactions of a series of acetates with Cl atoms. Atmos. Environ. 39, 5091–5099 (2005)

    Article  Google Scholar 

  • Frisch, M.J., Trucks, G.W., Schlegel, H.B., Scuseria, G.E., Robb, M.A., Cheeseman, J.R., Scalmani, G., Barone, V., Mennucci, B., Petersson, G.A. et al.: Gaussian 09, Revision B.01.; Gaussian, Inc.: Wallingford, CT (2010)

  • Garrett, B.C., Truhlar, D.G., Grev, R.S., Magnuson, A.W.: Improved Treatment Of Threshold Contributions In Variational Transition-State Theory. J. Phys. Chem. 84, 1730–1748 (1980)

    Article  Google Scholar 

  • Gonzalez-Lafont, A., Truong, T.N., Truhlar, D.G.: Interpolated Variational Transitionstate Theory: Practical Methods for Estimating Variational Transitionstate Properties and Tunneling Contributions to Chemical Reaction Rates from Electronic Structure Calculations. J. Chem. Phys. 95, 8875–8894 (1991)

    Article  Google Scholar 

  • Harley, R.A., Cass, G.R.: Modeling the atmospheric concentrations of individual volatile organic compounds. Atmos. Environ. 29, 905–922 (1995)

    Article  Google Scholar 

  • Hertz, H.S., Hites, R.A., Biemann, K.: Identification of Mass Spectra by Computer-searching a file of known spectra. J. Anal. Chem. 43, 681–691 (1971)

    Article  Google Scholar 

  • Holzinger, R., Warneke, C., Hansel, A., Jordan, A., Lindinger, W., Scharffe, D.H., Schade, G., Crutzen, P.J.: Biomass burning as a source of formaldehyde, acetaldehyde, methanol, acetone, acetonitrile, and hydrogen cyanide. Geophys. Res. Lett. 26(8), 1161–1164 (1999)

    Article  Google Scholar 

  • Jørgensen, S., Andersen, V.F., Nilsson, E.J., Nielsen, O.J., Johnson, M.S.: Theoretical study of the gas phase reaction of methyl acetate with the hydroxyl radical: Structures, mechanisms, rates and temperature dependencies. Chem. Phys. Lett. 490, 116–122 (2010)

    Article  Google Scholar 

  • Langer, S., Ljungström, E., Wängberg, I.: Rates of reaction between the nitrate radical and some aliphatic esters. J. Chem. Soc., Faraday Trans. 89(3), 425–431 (1993)

  • Le Calvé, S., Le Bras, G., Mellouki, A.: Kinetic studies of OH reactions with a series of methyl esters. J. Phys. Chem. A 101, 9137–9141 (1997)

    Article  Google Scholar 

  • Mellouki, A., Le Bras, G., Sidebottom, H.: Kinetics and mechanisms of the oxidation of oxygenated organic compounds in the gas phase. Chem. Rev. 103, 5077–5096 (2003)

    Article  Google Scholar 

  • Notario, A., Le Bras, G., Mellouki, A.: Absolute rate constants for the reactions of Cl atoms with a series of esters. J. Phys. Chem. A 102, 3112–3117 (1998)

    Article  Google Scholar 

  • Page, J.; McIver. “On Evaluating the Reaction Path Hamiltonian,” J. Chem. Phys. 88, 922–935 (1988)

  • Prinn, R.G., Weiss, R.F., Miller, B.R., Huang, J., Alyea, F.N., Cunnold, D.M., Fraser, P.J., Hartley, D.E., Simmonds, P.G.: Atmospheric Trends and Lifetime of CH3CCl3 and Global OH Concentrations. Science 269, 187–192 (1995)

    Article  Google Scholar 

  • Schütze, N., Zhong, X., Kirschbaum, S., Bejan, I., Barnes, I., Benter, T.: Relative kinetic measurements of rate coefficients for the gas-phase reactions of Cl atoms and OH radicals with a series of methyl alkyl esters. Atmos. Environ. 44, 5407–5414 (2010)

    Article  Google Scholar 

  • Singh, H.B., Thakur, A.N., Chen, Y.E., Kanakidou, M.: Tetrachloroethylene as an indicator of low Cl atom in the troposphere. Geophys. Res. Lett. 23, 1529–1532 (1996)

    Article  Google Scholar 

  • Souza, S.R., Vasconcellos, P.C., Carvalho, L.R.: Low molecular weight carboxylic acids in an urban atmosphere: Winter measurements in Sao Paulo City. Brazil. Atmos. Environ. 33, 2563–2574 (1999)

    Article  Google Scholar 

  • Spicer, C.W., Chapman, E.G., Finlayson-Pitts, B.J., Plastridge, R.A., Hubbe, J.M., Fast, J.D., Berkowitz, C.M.: Unexpectedly high concentrations of molecular chlorine in coastal air. Nature 394, 353–356 (1998)

    Article  Google Scholar 

  • Teruel, M.A., Benitez-Villalba, J., Caballero, N., Blanco, M.B.: Gas-Phase oxidation of methyl crotonate and ethyl crotonate. kinetic study of their reactions toward OH radicals and Cl atoms. J. Phys. Chem.A. 116(24), 6127–6133 (2012)

  • Truhlar, D.G., Kupperman, A.: Exact tunneling calculations. J. Am. Chem. Soc. 93, 1840–1851 (1971)

    Article  Google Scholar 

  • Veres, P., Roberts, J.M., Warneke, C., Welsh-Bon, D., Zahniser, M., Herndon, S., Fall, R. de., Gouw, J.: Development of negative-ion proton-transfer chemical-ionization mass spectrometry (NI-PT-CIMS) for the measurement of gas-phase organic acids in the atmosphere. Int. J. Mass Spectrom. 274, 48–55 (2008)

  • Wallington, T.J., Dagaut, P., Liu, R., Kurylo, M.J.: The gas phase reactions of hydroxyl radicals with a series of esters over the temperature range 240–440 K. Int. J. Chem. Kinet. 20, 177–186 (1988)

    Article  Google Scholar 

  • Xing, J.-H., Takahashi, K., Hurley, M.D., Wallington, T.J.: Kinetics of the reactions of chlorine atoms with a series of acetates. Chem. Phys. Lett. 474, 268–272 (2009)

    Article  Google Scholar 

  • Yujing, M., Mellouki, A.: Temperature dependence for the rate constants of the reaction of OH radicals with selected alcohols. Chem. Phys. Lett. 333, 63–68 (2001)

    Article  Google Scholar 

  • Zhang, K.M., Wexler, A.S., Zhu, Y.F., Hinds, W.C., Sioutas, C.: Evolution of particle number distribution near roadways. Part II: the ‘Road-to-Ambient’ process. Atmos. Environt 38, 6655–6665 (2004)

  • Zheng, J., Bao, J.L., Meana-Pañeda, R., Zhang, S., Lynch, B.J., Corchado, J.C., Chuang, Y.-Y., Fast, P.L., Hu, W.-P., Liu, Y.-P., et al.: Polyrate–version 2016–2A. University of Minnesota, Minneapolis (2016)

    Google Scholar 

Download references

Acknowledgments

The authors would like to acknowledge Mr. V. Ravichandran and Gayathri and HPCE, Indian Institute of Technology Madras for providing supercomputing facility.

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  1. Department of Chemistry, Indian Institute of Technology Madras, Chennai, India, 600036

    Ramya Cheramangalath Balan & Rajakumar Balla

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  1. Ramya Cheramangalath Balan
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Cheramangalath Balan, R., Balla, R. Kinetics for the photo-chemical degradation of Methyl butyrate in presence of Cl atoms and OH radicals. J Atmos Chem 78, 219–238 (2021). https://doi.org/10.1007/s10874-021-09417-w

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